Citation: Xiu-Fang HOU, Chuan BAI, Ya-Lei CAO, Feng FU. Boron Group Ions Direct Conversion of Carbon and Methane into Ethylene in DFT Study[J]. Chinese Journal of Structural Chemistry, ;2020, 39(2): 255-262. doi: 10.14102/j.cnki.0254–5861.2011–2453 shu

Boron Group Ions Direct Conversion of Carbon and Methane into Ethylene in DFT Study

Xiu-Fang HOU ^a,, ,
Chuan BAI ^a ,
Ya-Lei CAO ^b ,
Feng FU ^a

a.
Laboratory of Analytical Technology and Detection, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an 716000, China
b.
Qiushi Honors College, Tianjin University, Tianjin 300350, China

Corresponding author: Xiu-Fang HOU, houxf1977@126.com
Received Date: 13 May 2019
Accepted Date: 5 September 2019

Fund Project: the special steady growth science and technology foundation of Yanan Science and Technology Bureau 2017WZZ-08the doctoral research program YDBK2017-09the research program YD2016-09the research program D2018009

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In this study, density functional theory calculations reveal how boron group ions M⁺ (M = B, Al, Ga, In, and Tl) directly convert carbon and methane into ethylene at room temperature. M⁺ reacts with the carbon atom to form the cation MC⁺. Then, the reaction of MC⁺ with methane leads to the cleavage of metal–carbon bond and the formation of CH₂CH₂ through C–C coupling, with the ion M⁺ serving as a leaving group. The cycle then begins again. The mechanism of C/CH₄ system catalyzed by five ion types is investigated herein, and the reasons for the different reactivity of five ion types are determined. The moderate strength of the Al⁺–C bond results in Al⁺ being the only appropriate catalyst of M⁺ (M = B, Al, Ga, In, and Tl) that can catalyze methane and carbon into ethylene.
- boron group ion,
- C–C coupling,
- DFT,
- ethylene
1. [1]
  Ravi, M.; Ranocchiari, M.; Jeroen, A. van Bokhoven. The direct catalytic oxidation of methane to methanol-a critical assessment. Angew. Chem. Int. Ed. 2017, 56, 16464−16483. doi: 10.1002/anie.201702550
2. [2]
  Guo, X.; Fang, G.; Li, G.; Ma, H.; Fan, H.; Yu, L.; Ma, C.; Wu, X.; Deng, D.; Wei, M.; Tan, D.; Si, R.; Zhang, S.; Li, J.; Sun, L.; Tang, Z.; Pan, X.; Bao, X. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 2014, 344, 616−619. doi: 10.1126/science.1253150
3. [3]
  BP Energy Outlook (2018 edition). https://www.bp.com/en/global/corporate/energy-economics/energy-outlook.html.
4. [4]
  Leonori, F.; Skouteris, D.; Petrucci, R.; Casavecchia, P.; Rosi, M.; Balucani, N. Combined crossed beam and theoretical studies of the C(¹D) + CH₄ reaction. J. Chem. Phys. 2013, 138, 024311−11. doi: 10.1063/1.4773579
5. [5]
  Jeong, G. H.; Klabunde, K. J.; Pan, O. G.; Paul, G. C.; Shevlin, P. B. Reactions of carbon atoms/clusters with methane, methyl bromide, and water at 10 and 77 K. J. Am. Chem. Soc. 1989, 111, 8784−8790. doi: 10.1021/ja00206a003
6. [6]
  Kim, G. S.; Nguyen, T. L.; Mebel, A. M.; Lin, S. H.; Nguyen M. T. Ab Initio/RRKM study of the potential energy surface of triplet ethylene and product branching ratios of the C(³P) + CH₄ reaction. J. Phys. Chem. A 2003, 107, 1788−1796.
7. [7]
  Yue, L.; Li, J. L.; Zhou, S. D.; Sun, X. Y.; Schlangen, M.; Shaik, S.; Schwarz, H. Control of product distribution and mechanism by ligation and electric field in the thermal activation of methane. Angew. Chem. Int. Ed. 2017, 56, 10219−10223. doi: 10.1002/anie.201703485
8. [8]
  Yue, L.; Zhou, S.; Sun, X.; Schlangen, M.; Schwarz, H. Direct room-temperature conversion of methane to protonated formaldehyde: the gas-phase chemistry of mercury among the zinc triad oxide cations. Angew. Chem. Int. Ed. 2018, 57, 3251−3255. doi: 10.1002/anie.201712405
9. [9]
  Li, J.; Zhou, S.; Schlangen, M.; Weiske, T.; Schwarz, H. Hidden hydride transfer as a decisive mechanistic step in the reactions of the unligated gold carbide [AuC]⁺ with methane under ambient conditions. Angew. Chem. 2016, 128, 13266−13269. doi: 10.1002/ange.201606707
10. [10]
  Geng, C.; Li, J.; Weiske, T.; Schlangen, M.; Shaik, S.; Schwarz, H. Electrostatic and charge-induced methane activation by a concerted double C−H bond insertion. J. Am. Chem. Soc. 2017, 139, 1684−1689. doi: 10.1021/jacs.6b12514
11. [11]
  Zhou, S.; Li, J.; Schlangen, M.; Schwarz, H. Differences and commonalities in the gas-phase reactions of closed-shell metal dioxide clusters [MO₂]⁺ (M = V, Nb, and Ta) with methane. Chem. Eur. J. 2016, 22, 7225−7228. doi: 10.1002/chem.201600498
12. [12]
  Sun, X.; Zhou, S.; Yue, L.; Schlangen, M.; Schwarz, H. Thermal activation of CH₄ and H₂ as mediated by the ruthenium-oxide cluster ions [RuO_x]⁺ (x = 1~3): on the influence of oxidation states. Chem. Eur. J. 2019, 25, 1−11. doi: 10.1002/chem.201806054
13. [13]
  Geng, C.; Weiske, T.; Li, J.; Shaik, S.; Schwarz, H. On the intrinsic reactivity of diatomic 3d transition-metal carbides in the thermal activation of methane: striking electronic structure effects. J. Am. Chem. Soc. 2018, 141, 599−610.
14. [14]
  Kang, Y. K.; Park, H. S. Assessment of CCSD(T), MP2, DFT-D, CBS-QB3, and G4(MP2) methods for conformational study of alanine and proline dipeptides. Chem. Phy. Lett. 2014, 600, 112−117. doi: 10.1016/j.cplett.2014.03.067
15. [15]
  Pollak, P.; Weigend, F. Segmented contracted error-consistent basis sets of double- and triple‑ζ valence quality for one- and two-component relativistic all-electron calculations. J. Chem. Theory Comput. 2017, 13, 3696−3705. doi: 10.1021/acs.jctc.7b00593
16. [16]
  Becke, A. D. Density-functional thermochemistry. Ⅲ. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648−5652. doi: 10.1063/1.464913
17. [17]
  Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098−3100. doi: 10.1103/PhysRevA.38.3098
18. [18]
  Lee, C.; Yang, W. T.; Parr, R. G. Development of the Colle-Salvetti correlation energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785−789. doi: 10.1103/PhysRevB.37.785
19. [19]
  Andrae, D.; Häubermann, U.; Dolg, M.; Stoll, H.; Preub, H. Energy-adjusted ab initio pseudopotentials for the second and third row transition elements. Theor. Chim. Acta 1990, 77, 123−141. doi: 10.1007/BF01114537
20. [20]
  John, A.; Martin, H. G. Quadratic configuration interaction: a general technique for determining electron correlation energies. J. Chem. Phys. 1987, 87, 5968−5975. doi: 10.1063/1.453520
21. [21]
  Gonzalez, C.; Schlegel, H. B. An improved algorithm for reaction path following. J. Chem. Phys. 1989, 90, 2154−2161. doi: 10.1063/1.456010
22. [22]
  Reed, A. E.; Weinstock, R. B.; Weinhold, F. Natural population analysis. J. Chem. Phys. 1985, 83, 735−746. doi: 10.1063/1.449486
23. [23]
  Carpenter, J. E.; Weinhold, F. Analysis of the geometry of the hydroxymethyl radical by the different hybrids for different spins natural bond orbital procedure. J. Mol. Struct. (Theochem. ) 1988, 169, 41−62. doi: 10.1016/0166-1280(88)80248-3
24. [24]
  Lu, T.; Chen, F. Multiwfn: a multifunctional wave function analyzer. J. Comput. Chem. 2012, 33, 580−592. doi: 10.1002/jcc.22885
25. [25]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Annenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT 2013, Gaussian 09, Revision E. 01.
26. [26]
  Luo, Y. R. Comprehensive Handbook of Chemical Bond Energies. CRC Press Inc, Boca Raton, FL 2007, 1−1687.
27. [27]
  Lu, T.; Chen, F. Atomic dipole moment corrected Hirshfeld population method. J. Theor. Comput. Chem. 2012, 11, 163−183. doi: 10.1142/S0219633612500113
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